Dyeing of regenerated cellulose material



Patented May 6, 1936 UNITED. STATES, PATENT oFmca JAMES BADDILEY, OFBIAGKLEY, MANCHESTER, ENG-LAND, ASSIGNOR TO BRITISH DYESTUFFSCORPORATION LIMITED, 01 MANCHESTER, ENGLAND DYEING, OF REGENERATEDOELLULOSE MATERIAL I No Drawing. Original application filed ma 21, 1927,Serial No. 193,387, and in Great Britain December 10, 1926. Divided andthis application filed March 8, 1928, Serial N'o. 260,249. Renewed July6, 1929.

The invention relates to processes for the production of regeneratedcellulose products dyed in even level shades with the new secondarydisazo dyes described in my co-pendingspecification Serial No. 193,387,of which the present application is a division. These dyestufis are notwell suited for the commercial dyeing of cotton for while they dopossess a certain aflinity for cotton the aiiinity is in an inferiordegree, making the dyes, in

- view of the present state of the art, of little or no industrialinterest as cotton dyes. On the other hand I have discovered that inspite of this slight aflinity for cotton there is inherent in these dyesa valuable affinity for regenerated cellulose. Regenerated cellulosematerials are dyed in even level shades by these dyes.

These new secondary disazo dyes are obtained by combining the diazocompound of a paramtroarylamine, including a deriva tive thereof in thisterm, containing at least' one solubilizing acidic substituent, such asa sulphonic or carboxylic group, with any usual middle component,rediazotizing and combining with an amino naphthol sulphonic acid,including thesame in this term.

A small number of dyestufi's of this class have already been described,for-example, in British Patents Nos. 47 67/09, .47 68/09,

11364/09, but inall thesepreviously known examples the end componentsused have been 2-amino-5-naphthol-7-sulphonic acid or its N-alkyl, arylor acyl derivatives, or with substitutlon products of these compoundssubstituted in. the ortho position to the amino group. Itis well knownthat in the application of ordinary blue cotton dyes to regeneratedcellulose in the form of artificial silk there is great diflicultamounting at times to impossibility, in o taining level shades.

I therefore specifically except from my mi to the boil. The goods a thenremoved in the said specifications, and other substitution products of2-amino-5-naphthol 7-sul- N-substitution products of phonic acidsubstituted in the ortho position l gdyed, owing to the variable avidityof the fiber for these dyestuffs. The aflinity for regenerated celluloseof my new dyestuffs obtained according to the disclosure in mapplication Ser. N 0. 193,387 and whic as stated, yield blue shades, isof a nature differing from that of ordinary cotton-dyes and is such thatdyeings of a very superior degree of levelness and evenness may beproduced on such regenerated cellulose materials. The present inventionis an important advance in the production of dyed regenerated cellulosematerials having even level shades.

The present invention is limited to dyeing regenerated cellulosematerials in even level shades with dyes'obta'ined by coupling an aminonaphthol sulphonic acid in which the shortest .chain between thenitrogen atom and the oxygen of the hydroxyl group comprises less thanfive atoms. These dyes may e represented by the general formula I 01-I-n -'N'=1-I'--R,--N='i-I-Ra wherein R represents a divalent arylresi.- due containing at leastone solubilizing acidic group, Rrepresentsa divalent aryl residue and R5 represents a coupled aminonaphthol sulphonic acid in which the shortest chain between the nitrogenatom and the oxygen of the hydroxyl group comprises less than '5 atomsand in which the nitro group is attached to R in para position to theazo group- -In practising my invention, the dyestufi-is dissolved inwarmwater, with or without the adjunctsusual for dye-baths, and theregeneratedcellulose material is entered into the warm bath which isthen raised nearly rinsed and dried.

Inorder to further illustrate-the invenfollowing conditions beingtypical, but I do not limitmyself to the conditions herede scribed.

The dye-bath is made up from 3,000 artsof water, 3 parts of soap, 15parts of Glau ers salt and one part of the dyestufi having the formula Iom N.'N v v I I .No es. N:N

om H NH:

which may be obtained as described in 00-.

pending application Serial No. 193,387 100 parts of the regeneratedcellulose silk are entered into the bath at about 40 C. and the bath isthen raised nearly to boiling, the dyeing being thencontinued for aboutone hour.

The goods are then removed, rinsed and dried. The fabric is dyed a levelbright blue shade, fast to light and to alkalies. What I claim anddesire to secure by Letters Patent is 1. The process of dyeingregenerated cellulose materials in even level shades which comprisesapplying thereto disazo dyes obtained by coupling the diazo compound ofa p-nitro arylamine containing at least one solubilizing acidic groupwith a primary arylamine which Nzlq N0 -SthNa N:N I om n m 3. Theprocess of dyein regenerated cellulose materials in even leve shadeswhich comprises aoplying to said regenerated cellulose material thesecondary disazo dyes having the general formula om-n.N=N-a,- N '1-i'n.wherein R represents a divalent aryl residue containing at least .onesolubilizing acidic group, R 'represents a divalent aryl residue and 3sulphonic acid in whic the shortest chain between the nitrogen atom andthe oxygen of the hydroxyl group comprises less than 5 carbon atoms andin which the nitro group is attached to R in para position to the am- 4.The process of dyeing regenerated cellulose materials in even levelshades which comprises applying to said regenerated cellulose representsa con led amino naphthol material the secondary disazo dyes having thegeneral formula 0aNR;N=NR|-N=N-R4 wherein R represents a divalent arylresidue containing at least one solubilizing acidic group, R representsa divalent aryl residue andR represents a coupled 1': S-amino naphtholsulphonic acid and in which the-nitro group is attached to R in paraposition to the Mo group.

5. The process of dyeing regenerated cellulose materials in even levelshades which comprises applying to said regenerated cellulose materialthe secondary disazo dyes having the general formula wherein Rrepresents a divalent aryl residue containing a sulphonic acid group, Rrepresentsa divalent aryl residue and R represents a coupled 1: 8-aminonaphthol sulplionic acid and in which the nitro group it attached to R,in para position to the am gmup.

6. The process of dyeing regenerated cellu lose materials in-even levelshades which comthe general formula wherein R represents a divalent arylresidue and R represents a coupled 1 8-amino naphthol sulphonic acid.

7. Regeneratedcellulose materials dyed with the secondary disazo dyeshaving the wherein R represents adivalent aryl residue containing atleast one solubilizing acidic group, R represents a divalent arylresidue and 5 represents a coupled amino naphthol sulphonic acid inwhich the shortest chain between the nitrogen atom and the oxygen of thehydroxyl group comprises less than 5 carbon atoms and in which the nitrogroup is attached to il terials having an even level shade.

in para position to the amgroup, the said regenerated cellulose ma- '90prises applying to said regenerated cellulose material the secondarydisazo dyes having" 8. Regenerated cellulosematerials dyed with thesecondary disazo dyes having the general formula .wherein R represents adivalent aryl residue containing at least one solubilizing acidic grou Rrepresents a divalent aryl residue and 4 re resents a coupled 1 8-aminonaphthol sulp onic acid and in which the nitro group is attached to R inpara position to the azo group, the said regenerated cellulose materlalshaving an even level shade.

9. Regenerated cellulosic materials dyed with the secondary disaz'o dyeshaving the general formula v wherein R represents a divalent arylresidue containing a sulphonic acid group, R represents a divalent arylresidue and R represents a coupled 1:8-amino jnaphthol sulphonic acidand in which the nitro group is attached to R in para position to theazo group, the said regenerated cellulose materials having an even levelshade.

10. Regenerated cellulose materials dyed with thesecondary disazo dyeshaving the general formula wherein R represents a divalent aryl residueand R represents a coupled 1:8-amino naphthol sulphonic acid, the saidregenerated cellulose materials having an even level shade.

11. Regenerated cellulose materials dyed with the secondary disazo dyeshaving the general formula on. SOzNa N0 some N N on, H NH:

the said regenerated cellulose materials havin an even level shade.

testimony whereof I aflix my signature.

JAMES BADDILEY.

